CN109748595B - Mixed permeating agent, application and reaction infiltration preparation method - Google Patents
Mixed permeating agent, application and reaction infiltration preparation method Download PDFInfo
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- CN109748595B CN109748595B CN201711053337.9A CN201711053337A CN109748595B CN 109748595 B CN109748595 B CN 109748595B CN 201711053337 A CN201711053337 A CN 201711053337A CN 109748595 B CN109748595 B CN 109748595B
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Abstract
The invention provides a mixed infiltration agent, application and a reaction infiltration preparation method, wherein ceramic particles with melting points higher than reaction infiltration temperature and non-reacting with carbon and silicon in the range from normal temperature to melting points are doped in the infiltration agent to obtain the surface self-cleaning effect of an infiltration member, thereby realizing net size forming of complex members prepared by infiltration. The invention increases the volume of the penetrating agent by configuring the mixed penetrating agent, is more suitable for silicon distribution by an embedding method, and simplifies the silicon distribution mode of a complex component.
Description
Technical Field
The invention relates to a mixed infiltration agent, application and a reaction infiltration preparation method, and belongs to the technical field of composite material reaction infiltration preparation.
Background
The carbon fiber or silicon carbide fiber reinforced silicon carbide-based composite material has the characteristics of oxidation resistance, light weight, thermal shock resistance, excellent high-temperature performance and the like, so that the carbon fiber or silicon carbide fiber reinforced silicon carbide-based composite material is widely applied to the fields of aviation, aerospace, automobiles and the like. At present, the manufacturing process technology of the composite material mainly comprises 3 types: vapor phase infiltration (CVI), precursor pyrolysis (PIP) and reactive infiltration (RMI).
RMI is a C/SiC material obtained by impregnating a C/C porous body with liquid Si. Compared with the C/C composite material, the C/SiC composite material prepared by the RMI process has the advantages of strong thermal shock resistance, medium strength, good oxidation resistance, good friction performance at low temperature, no influence of environmental humidity, stable friction coefficient and the like. Compared with CVI and PIP processes, the RMI process has the advantages of short preparation period, low cost, low residual porosity (2-5 percent) and the like, and is an industrial production technology with market competitiveness. However, when the C/SiC composite material is prepared by adopting the RMI process, silicon is generally distributed in an embedding mode, and a large amount of residual silicon is attached to the surface of a component after reaction infiltration. For some profiles that are not easy to machine (e.g., deep cavities, internal profiles, etc.), the RMI process does not meet the net shape forming requirements.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, realize the net size forming of a C/SiC component, and provide a mixed infiltration agent, an application and an RMI preparation method capable of realizing that no residual silicon exists on the surface of the component after infiltration, namely the surface is self-cleaned.
The technical solution of the invention is as follows: a mixed penetrating agent is composed of silicon powder and ceramic particles, wherein the volume ratio of the silicon powder to the ceramic particles is as follows: ceramic fine particles 1: (0.5 to 5) the melting point T of the ceramic fine particlesr≥TSi+50 ℃ wherein T isSiThe temperature is the infiltration reaction temperature of the silicon powder, and the ceramic particles do not react with carbon and silicon within the range from normal temperature to melting point.
The volume ratio of the mixed penetrating agent (silicon powder: ceramic particles) is 1: (0.5-5), if the volume ratio of the ceramic particles is too small, the self-cleaning effect is not obvious, and if the volume ratio is too high, the capillary adsorption effect of infiltration is influenced, and the infiltration efficiency is reduced; the change within the range of the requirements has no obvious influence on the subsequent infiltration efficiency and the self-cleaning effect.
The ceramic particles are Al2O3、ZrO2、HfO2SiC, ZrC or TaC. However, the ceramic fine particles are not limited thereto, and may be any ceramic fine particles that can satisfy the above-mentioned melting point and reactivity requirements.
The silicon powder used in the invention is micro-nano grade and adopts a commercial product. In the mixed permeating agent, the diameter of the ceramic particles is preferably 0.1-2 mm, the ceramic particles smaller than 0.1mm are easy to adsorb on the surface of the member to cause hole blocking, and the self-cleaning effect of the surface of the member is not good when the diameter is larger than 2 mm.
In the invention, ceramic particles which do not react with carbon and silicon are added into silicon powder, and during the infiltration reaction, the ceramic particles limit the enrichment of unreacted molten silicon on the surface of a component (as shown in figure 1), so as to achieve the effect of self-cleaning the surface and realize the net-size forming of the component.
A mixed penetrant composed of silicon powder and ceramic particles is used for preparing carbide-base composite material by reaction and dissolving-permeating process.
The silicon powder and the ceramic particles are mixed according to the volume ratio of 1: (0.5-5) are mixed uniformly.
A reaction infiltration preparation method is realized by the following steps:
the first step, preparing the C/C composite material,
the density of the C/C composite material in the step cannot be too high, and the density is preferably 1.2-1.6 g/cm3。
The C/C composite material can be prepared by adopting a known technology, and can be prepared by processes such as chemical vapor deposition, precursor carbonization treatment and the like.
The density of the composite material is lower than 1.2g/cm3When the method is used, the porosity is high, so that enough reaction infiltration space is provided for subsequent siliconizing, but the obtained material has poor mechanical property; the density of the composite material is higher than 1.6g/cm3When the method is used, the porosity is low, and the subsequent siliconizing treatment is not facilitated. The density of the composite material is most preferably 1.4 +/-0.5 g/cm3Within the range, the comprehensive performance is optimal; when the density of the composite material is lower than the most preferable range, the lower the density of the composite material is, the higher the silicon content in the final product is after siliconizing, and the lower the mechanical property is; when the density of the composite material is higher than the above preferred range, the higher the density of the composite material is, the less the density increases after siliconizing treatment, and the lower the density of the final product is, the lower the mechanical properties are.
The second step, preparing a mixed permeating agent,
silicon powder and one or more ceramic particles are uniformly mixed to prepare a mixed penetrating agent, and the volume ratio of the mixed penetrating agent is silicon powder: ceramic fine particles 1: (0.5 to 5);
and thirdly, carrying out high-temperature infiltration to obtain the C/SiC composite material.
High temperature infiltration reactions are well known in the art and those skilled in the art will be able to determine the optimum infiltration process parameters for a particular production practice.
Further, the present invention provides a more preferable infiltration process, specifically as follows:
a3.1, high-temperature treatment before infiltration,
heating the C/C composite material embedded with the mixed permeating agent to 20-70 ℃ above the melting temperature of silicon in inert atmosphere, and preserving heat for 1.5-2 hours;
in the step, the silicon powder is heated to a melting state under the effect of heat preservation for 1.5-2 hours at the temperature 20-70 ℃ above the melting temperature of the silicon, and the heat preservation is set to ensure the uniform temperature of the component. By adopting the step, the loss caused by vaporization of the silicon powder before the high-temperature infiltration is avoided, and the uniform temperature of the large-size component is beneficial to eliminating the stress concentration problem generated in the temperature rise. Within the above-mentioned range of requirements, it has no obvious influence on the subsequent infiltration reaction.
The skilled person will select a suitable temperature and incubation time within the above ranges depending on the actual production. The step has no special requirement on the heating rate, and is determined according to the equipment capacity and the structural characteristics of the component, so that the component is controlled not to generate stress deformation.
And A3.2, continuously heating the composite material subjected to high-temperature treatment before infiltration in the step A3.1 to the infiltration temperature, preserving the heat, and completing the high-temperature infiltration reaction to obtain the C/SiC composite material.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention increases the volume of the penetrating agent by configuring the mixed penetrating agent, is more suitable for silicon distribution by an embedding method, and simplifies the silicon distribution mode of a complex component;
(2) the invention realizes the preparation of the surface self-cleaning component by the reaction infiltration because the addition of the ceramic particles limits the enrichment of unreacted molten silicon on the surface of the component;
(3) the invention adopts the ceramic particles which are not reacted with carbon and silicon to be mixed into the silicon powder, thereby achieving the effect of self-cleaning the surface and realizing the net size forming of the component.
Drawings
FIG. 1 is a schematic diagram of the present invention;
FIG. 2 is a flow chart of the present invention.
Detailed Description
The present invention will be described in detail with reference to specific examples.
The invention provides a mixed penetrating agent, which consists of silicon powder and ceramic particles, wherein the volume ratio of the silicon powder to the ceramic particles is as follows: ceramic fine particles 1: (0.5 to 5) the melting point T of the ceramic fine particlesr≥TSi+50 ℃ wherein T isSiThe temperature is the infiltration reaction temperature of the silicon powder, and the ceramic particles do not react with carbon and silicon within the range from normal temperature to melting point.
Further, the invention also provides a reaction infiltration preparation method as shown in fig. 2, which comprises the steps of preparing the C/C composite material, preparing the mixed infiltration agent meeting the requirements, and carrying out high-temperature infiltration to obtain the C/SiC component with a self-cleaning surface.
Example 1
Loading the carbon fiber preform into a CVI-C furnace, and introducing C under the conditions of vacuum and 1020 DEG C3H8And mixing with Ar mixed gas, depositing for 180 hours, and discharging. Performing high-temperature treatment at 1700 ℃, adopting ammonia phenolic aldehyde precursor impregnant, performing vacuum impregnation-pressure curing-high-temperature cracking at 800 ℃, and preparing the product with the density of 1.40g/cm3The C/C composite material of (1). Silicon powder and alumina particles (diameter 0.5mm) are adopted in a volume ratio of 1: 1, and embedding the C/C composite material by adopting a mixed permeating agent, wherein the mass ratio of silicon to the C/C composite material in the mixed permeating agent is 2: 1, heating to 1450 ℃ in vacuum, preserving heat for 100min, then raising to 1700 ℃ in 1 hour, and preserving heat for 60min to prepare the C/SiC composite material with self-cleaning surface and the density of 2.1g/cm3The flexural strength was 246 MPa.
Example 2
Loading the carbon fiber preform into a CVI-C furnace, and introducing C under the conditions of vacuum and 1020 DEG C3H8And mixing with Ar mixed gas, depositing for 180 hours, and discharging. Performing high-temperature treatment at 1700 ℃, adopting ammonia phenolic aldehyde precursor impregnant, performing vacuum impregnation-pressure curing-high-temperature cracking at 800 ℃, and preparing the product with the density of 1.25g/cm3The C/C composite material of (1). The volume ratio of silicon powder to zirconia particles (diameter 1mm) is 1: 0.5, and embedding the C/C composite material by adopting a mixed permeating agent, wherein the mass ratio of silicon in the mixed permeating agent to the C/C composite material is 2: 1, heating to 1450 ℃ in vacuum, preserving heat for 100min, then raising to 1700 ℃ in 1 hour, and preserving heat for 60min to prepare the C/SiC composite material with self-cleaning surface and the density of 2.3g/cm3The flexural strength was 225 MPa.
Example 3
Loading the carbon fiber preform into a CVI-C furnace, and introducing C under the conditions of vacuum and 1020 DEG C3H8And mixing with Ar mixed gas, depositing for 180 hours, and discharging. Performing high-temperature treatment at 1700 ℃, adopting ammonia phenolic aldehyde precursor impregnant, performing vacuum impregnation-pressure curing-high-temperature cracking at 800 ℃, and preparing the product with the density of 1.60g/cm3The C/C composite material of (1). The volume ratio of silicon powder to zirconium carbide particles and zirconium oxide particles (diameter 1mm) is 1: 5, and embedding the C/C composite material by adopting a mixed permeating agent, wherein the mass ratio of silicon to the C/C composite material in the mixed permeating agent is 2: 1, heating to 1450 ℃ in vacuum, preserving heat for 100min, then raising to 1700 ℃ in 1 hour, and preserving heat for 60min to prepare the C/SiC composite material with self-cleaning surface and the density of 1.85g/cm3The flexural strength was 162 MPa.
The invention has not been described in detail and is in part known to those of skill in the art.
Claims (7)
1. A mixed permeating agent is characterized in that: the silicon powder ceramic consists of silicon powder and ceramic particles, wherein the volume ratio of the silicon powder to the ceramic particles is as follows: ceramic fine particles 1: (0.5 to 5) the melting point T of the ceramic fine particlesr≥TSi+50 ℃ wherein T isSiThe temperature is the infiltration reaction temperature of the silicon powder, and the ceramic particles do not react with carbon and silicon within the range from normal temperature to melting point.
2. The mixed penetration agent according to claim 1, which is characterized in that: the ceramic particles are Al2O3、ZrO2、HfO2One or more of SiC, ZrC and TaC, and the diameter of the ceramic particles is 0.1-2 mm.
3. Use of the infiltrant mixture according to claim 1 for the preparation of a carbide-based composite material by a reactive infiltration process.
4. The reaction infiltration preparation method is characterized by comprising the following steps of:
the first step, preparing the C/C composite material,
the second step, preparing a mixed permeating agent,
silicon powder and one or more ceramic particles are uniformly mixed to prepare a mixed penetrating agent, and the volume ratio of the mixed penetrating agent is silicon powder: ceramic fine particles 1: (0.5 to 5) the melting point T of the ceramic fine particlesr≥TSi+50 ℃ wherein T isSiThe reaction temperature of silicon powder infiltration is set, and the ceramic particles do not react with carbon and silicon within the range from normal temperature to melting point;
and thirdly, carrying out high-temperature infiltration to obtain the C/SiC composite material.
5. The reactive infiltration preparation method of claim 4, wherein: the density of the C/C composite material in the first step is 1.2-1.6 g/cm3。
6. The reactive infiltration preparation method of claim 4, wherein: the density of the C/C composite material in the first step is 1.4 +/-0.5 g/cm3。
7. The reactive infiltration preparation method of claim 4, wherein: the third infiltration process comprises the following steps:
a3.1, high-temperature treatment before infiltration,
heating the C/C composite material embedded with the mixed permeating agent to 20-70 ℃ above the melting temperature of silicon in inert atmosphere, and preserving heat for 1.5-2 hours;
and A3.2, continuously heating the composite material subjected to high-temperature treatment before infiltration in the step A3.1 to the infiltration temperature, preserving the heat, and completing the high-temperature infiltration reaction to obtain the C/SiC composite material.
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| CN110937910B (en) * | 2019-12-13 | 2021-09-07 | 中南大学 | Preparation method of composite nano refractory ceramic modified carbon/carbon composite material |
| CN114605170A (en) * | 2022-04-13 | 2022-06-10 | 北航（四川）西部国际创新港科技有限公司 | Infiltration agent with multilayer coating structure and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1361755A (en) * | 1999-07-23 | 2002-07-31 | M丘比德技术公司 | Silicon carbide composites and methods for making same |
| CN103342570A (en) * | 2013-07-11 | 2013-10-09 | 山东宝纳新材料有限公司 | Method for preparing C/SiC composite material through low-cost fused silicon impregnation method |
| CN105541416A (en) * | 2016-01-18 | 2016-05-04 | 西北工业大学 | Preparation method for HfC-SiC coating on C/C composite material surface |
| CN106882974A (en) * | 2015-12-15 | 2017-06-23 | 航天特种材料及工艺技术研究所 | A kind of preparation method of HfC contents C/HfC-SiC composites high |
| CN107032816A (en) * | 2017-05-10 | 2017-08-11 | 西北工业大学 | A kind of silicon carbide nanometer line enhancing C/C SiC ZrB2The preparation method of ceramic matric composite |
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| EP1399396A2 (en) * | 2000-11-21 | 2004-03-24 | M Cubed Technologies Inc. | Boron carbide composite bodies, and methods for making same |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1361755A (en) * | 1999-07-23 | 2002-07-31 | M丘比德技术公司 | Silicon carbide composites and methods for making same |
| CN103342570A (en) * | 2013-07-11 | 2013-10-09 | 山东宝纳新材料有限公司 | Method for preparing C/SiC composite material through low-cost fused silicon impregnation method |
| CN106882974A (en) * | 2015-12-15 | 2017-06-23 | 航天特种材料及工艺技术研究所 | A kind of preparation method of HfC contents C/HfC-SiC composites high |
| CN105541416A (en) * | 2016-01-18 | 2016-05-04 | 西北工业大学 | Preparation method for HfC-SiC coating on C/C composite material surface |
| CN107032816A (en) * | 2017-05-10 | 2017-08-11 | 西北工业大学 | A kind of silicon carbide nanometer line enhancing C/C SiC ZrB2The preparation method of ceramic matric composite |
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